We present a new climatology of monthly air-sea oxygen fluxes throughout the ice-free surface global ocean. The climatology is based on weighted linear least squares regressions using heat flux monthly anomalies for spatial and temporal interpolation of historical O-2 data. The seasonal oceanic variations show that the tropical belt (20degreesS-20degreesN) is characterized by relatively small air-sea fluxes when compared to the middle to high latitudes (40degrees-70degrees). The largest and lowest seasonal fluxes occur during summer and winter in both hemispheres. By means of an atmospheric transport model we show that our climatology is in better agreement with the observed amplitude and phasing of the variations in atmospheric O-2/N-2 ratios because of seasonal air-sea exchanges at baseline stations in the Pacific Ocean than with previous air-sea O-2 climatologies. Our study indicates that the component of the air-sea O-2 flux that correlates with heat flux dominates the large-scale air-sea O-2 exchange on seasonal timescales. The contribution of each major oceanic basin to the atmospheric observations is described. The seasonal net thermal (SNOT) and biological (SNOB) outgassing components of the flux are examined in relation to latitudinal bands, basin-wide, and hemispheric contributions. The Southern Hemisphere's SNOB (similar to0.26 Pmol) and SNOT (similar to0.29 Pmol) values are larger than the Northern Hemisphere's SNOB (similar to0.15 Pmol) and SNOT (similar to0.16 Pmol) values (1 Pmol = 10(15) mol). We estimate a global extratropical carbon new production during the outgassing season of 3.7 Pg C (1 Pg = 10(15) g), lower than previous estimates with air-sea O-2 climatologies.

Two independent programs have collected and analyzed atmospheric CO2 samples from Point Barrow, Alaska, for radiocarbon content (Delta C-14) over the period 2003-2007. In one program, flask collection, stable isotope analysis, and CO2 extraction are performed by the Scripps Institution of Oceanography's CO2 Program and CO2 is graphitized and measured by accelerator mass spectrometry (AMS) at Lawrence Livermore National Laboratory. In the other program, the University of California, Irvine, performs flask collection, sample preparation, and AMS. Over 22 common sample dates spanning 5 yr, differences in measured Delta C-14 are consistent with the reported uncertainties and there is no significant bias between the programs.

High precision measurements of Delta C-14 were conducted for monthly samples of CO2 from seven global stations over 2- to 16-year periods ending in 2007. Mean Delta C-14 over 2005-07 in the Northern Hemisphere was 5 parts per thousand lower than Delta C-14 in the Southern Hemisphere, similar to recent observations from I. Levin. This is a significant shift from 1988-89 when Delta C-14 in the Northern Hemisphere was slightly higher than the South. The influence of fossil fuel CO2 emission and transport was simulated for each of the observation sites by the TM3 atmospheric transport model and compared to other models that participated in the Transcom 3 Experiment. The simulated interhemispheric gradient caused by fossil fuel CO2 emissions was nearly the same in both 1988-89 and 2005-07, due to compensating effects from rising emissions and decreasing sensitivity of Delta C-14 to fossil fuel CO2. The observed 5 parts per thousand shift must therefore have been caused by non-fossil influences, most likely due to changes in the air-sea C-14 flux in the Southern Ocean. Seasonal cycles with higher Delta C-14 in summer or fall were evident at most stations, with largest amplitudes observed at Point Barrow (71 degrees N) and La Jolla (32 degrees N). Fossil fuel emissions do not account for the seasonal cycles of Delta C-14 in either hemisphere, indicating strong contributions from non-fossil influences, most likely from stratosphere-troposphere exchange.

The isotopic composition of carbon (Delta C-14 and delta C-13) in atmospheric CO2 and in oceanic and terrestrial carbon reservoirs is influenced by anthropogenic emissions and by natural carbon exchanges, which can respond to and drive changes in climate. Simulations of C-14 and C-13 in the ocean and terrestrial components of Earth system models (ESMs) present opportunities for model evaluation and for investigation of carbon cycling, including anthropogenic CO2 emissions and uptake. The use of carbon isotopes in novel evaluation of the ESMs' component ocean and terrestrial biosphere models and in new analyses of historical changes may improve predictions of future changes in the carbon cycle and climate system. We compile existing data to produce records of Delta C-14 and delta C-13 in atmospheric CO2 for the historical period 1850-2015. The primary motivation for this compilation is to provide the atmospheric boundary condition for historical simulations in the Coupled Model Intercomparison Project 6 (CMIP6) for models simulating carbon isotopes in the ocean or terrestrial biosphere. The data may also be useful for other carbon cycle modelling activities.

High precision measurements of Delta C-14 were performed on CO2 sampled at La Jolla, California, USA over 1992-2007. A decreasing trend in Delta C-14 was observed, which averaged -5.5 parts per thousand yr(-1) yet showed significant interannual variability. Contributions to the trend in global tropospheric Delta C-14 by exchanges with the ocean, terrestrial biosphere and stratosphere, by natural and anthropogenic C-14 production and by C-14-free fossil fuel CO2 emissions were estimated using simple models. Dilution by fossil fuel emissions made the strongest contribution to the Delta C-14 trend while oceanic C-14 uptake showed the most significant change between 1992 and 2007, weakening by 70%. Relatively steady positive influences from the stratosphere, terrestrial biosphere and C-14 production moderated the decreasing trend. The most prominent excursion from the average trend occurred when Delta C-14 decreased rapidly in 2000. The rapid decline in Delta C-14 was concurrent with a rapid decline in atmospheric O-2, suggesting a possible cause may be the anomalous ventilation of deep C-14-poor water in the North Pacific Ocean. We additionally find the presence of a 28-month period of oscillation in the Delta C-14 record at La Jolla.

Development of radiocarbon analysis with precision better than 2%omicron has the potential to expand the utility of (CO2)-C-14 measurements for carbon cycle investigations as atmospheric gradients currently approach the typical measurement precision of 2-5%omicron. The accelerator mass spectrometer at Lawrence Livermore National Laboratory (LLNL) produces high and stable beam currents that enable efficient acquisition times for large numbers of C-14 counts. One million C-14 atoms can be detected in approximately 25 min, suggesting that near 1%omicron counting precision is economically feasible at LLNL. The overall uncertainty in measured values is ultimately determined by the variation between measured ratios in several sputtering periods of the same sample and by the reproducibility of replicate samples. Experiments on the collection of 1 million counts on replicate samples of CO2 extracted from a whole air cylinder show a standard deviation of 1.7%omicron in 36 samples measured over several wheels. This precision may be limited by the reproducibility of oxalic acid I standard samples, which is considerably poorer. We outline the procedures for high-precision sample handling and analysis that have enabled reproducibility in the cylinder extraction samples at the <2%omicron level and describe future directions to continue increasing measurement precision at LLNL.

Analysis systems incorporating atmospheric observations could provide a powerful tool for validating fossil fuel CO2 (ffCO(2)) emissions reported for individual regions, provided that fossil fuel sources can be separated from other CO2 sources or sinks and atmospheric transport can be accurately accounted for. We quantified ffCO(2) by measuring radiocarbon (C-14) in CO2, an accurate fossil-carbon tracer, at nine observation sites in California for three months in 2014-15. There is strong agreement between the measurements and ffCO(2) simulated using a high-resolution atmospheric model and a spatiotemporally-resolved fossil fuel flux estimate. Inverse estimates of total in-state ffCO(2) emissions are consistent with the California Air Resources Board's reported ffCO(2) emissions, providing tentative validation of California's reported ffCO(2) emissions in 2014-15. Continuing this prototype analysis system could provide critical independent evaluation of reported ffCO(2) emissions and emissions reductions in California, and the system could be expanded to other, more data-poor regions.

Seasonal variations of atmospheric carbon dioxide (CO2) in the Northern Hemisphere have increased since the 1950s, but sparse observations have prevented a clear assessment of the patterns of long-term change and the underlying mechanisms. We compare recent aircraft-based observations of CO2 above the North Pacific and Arctic Oceans to earlier data from 1958 to 1961 and find that the seasonal amplitude at altitudes of 3 to 6 km increased by 50% for 45 degrees to 90 degrees N but by less than 25% for 10 degrees to 45 degrees N. An increase of 30 to 60% in the seasonal exchange of CO2 by northern extratropical land ecosystems, focused on boreal forests, is implicated, substantially more than simulated by current land ecosystem models. The observations appear to signal large ecological changes in northern forests and a major shift in the global carbon cycle.

Measurements of Delta C-14 in atmospheric CO2 are an effective method of separating CO2 additions from fossil fuel and biospheric sources or sinks of CO2. We illustrate this technique with vertical profiles of CO2 and Delta C-14 analysed in whole air flask samples collected above Colorado, USA in May and July 2004. Comparison of lower tropospheric composition to cleaner air at higher altitudes (>5 km) revealed considerable additions from respiration in the morning in both urban and rural locations. Afternoon concentrations were mainly governed by fossil fuel emissions and boundary layer depth, also showing net biospheric CO2 uptake in some cases. We estimate local industrial CO2: CO emission ratios using in situ measurements of CO concentration. Ratios are found to vary by 100% and average 57 mole CO2:1 mole CO, higher than expected from emissions inventories. Uncertainty in CO2 from different sources was +/- 1.1 to +/- 4.1 ppm for addition or uptake of -4.6 to 55.8 ppm, limited by Delta 14C measurement precision and uncertainty in background Delta C-14 and CO2 levels.